WO2023118897A1 - Encre hélio exempte d'huile minérale - Google Patents

Encre hélio exempte d'huile minérale Download PDF

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Publication number
WO2023118897A1
WO2023118897A1 PCT/GB2022/053381 GB2022053381W WO2023118897A1 WO 2023118897 A1 WO2023118897 A1 WO 2023118897A1 GB 2022053381 W GB2022053381 W GB 2022053381W WO 2023118897 A1 WO2023118897 A1 WO 2023118897A1
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WO
WIPO (PCT)
Prior art keywords
ink
varnish
oil
intaglio
renewable
Prior art date
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PCT/GB2022/053381
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English (en)
Inventor
Vincent John FORRESTER
Original Assignee
Sun Chemical Corporation
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Filing date
Publication date
Application filed by Sun Chemical Corporation filed Critical Sun Chemical Corporation
Priority to EP22840280.6A priority Critical patent/EP4430132A1/fr
Priority to AU2022421027A priority patent/AU2022421027B2/en
Publication of WO2023118897A1 publication Critical patent/WO2023118897A1/fr
Priority to CONC2024/0009418A priority patent/CO2024009418A2/es

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/104—Polyesters
    • C09D11/105—Alkyd resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention describes a water wipe security intaglio printing ink composition
  • a water wipe security intaglio printing ink composition comprising as a principal component bio-renewable iso-alkane vegetable oil-based solvent, which in combination with other constituents produces a mineral oil-free ink with improved sustainability and environmental impact footprint when compared to existing formulations designed for the same application.
  • mineral oil is widely known and may be understood to refer to refined petroleum-based hydrocarbons.
  • a typical intaglio ink will contain up to 15% of mineral oil distillate such as Exxsol D60 (de-aromatised, low aromatic hydrocarbon solvent, distillation range 187-216°C).
  • intaglio ink compositions which contain reduced amounts of mineral oil and more preferably are free of mineral oil and not classified as VOC under 2010/75/EC directive and contain less than 1% VOC under 2004/42/EC directive, and are especially suited for the intaglio printing of security documents such as banknotes, passports and the like.
  • Modem intaglio ink formulations need to fulfil a complex range of requirements, which are significantly different to those for other paste inks used in offset and letterpress printing.
  • a rotating engraved steel cylinder carrying a pattern or image to be printed, and heated to a temperature of the order of 80°C, is supplied with ink by one or more schablones. Subsequent to the inking, any excess of ink on the plain surface of the printing cylinder is wiped off by a rotating wiping cylinder.
  • the remaining ink in the engraving of the printing cylinder is transferred under pressure onto the substrate to be printed, which may be a paper, polymeric or hybrid material in sheet or reel form, while the wiping cylinder is cleaned by a wiping solution, which is alkaline in nature and composed of mainly demineralised water normally containing between 0.6 to 1.0% sodium hydroxide (caustic soda) and approximately 0.5% of sulphonated castor oil.
  • a wiping solution which is alkaline in nature and composed of mainly demineralised water normally containing between 0.6 to 1.0% sodium hydroxide (caustic soda) and approximately 0.5% of sulphonated castor oil.
  • the film thickness of the ink transferred to the substrate can be varied from a few micrometers to several tens of micrometers by a correspondingly engraved printing plate. This ability to vary the film thickness is a most desirable feature of the intaglio printing process and the tactile feel of these relief effects is a strong security feature.
  • Intaglio ink formulations need to be able to print cleanly at high film thicknesses on intaglio presses, particularly on high speed sheetfed intaglio printing presses without causing “set off’ in the sheet stack.
  • the factors influencing ink drying and “set-off’ are determined by the printing ink formulation, the engraving depth and evenness, the printing conditions, the printing substrate, the number of stacked sheets per pile, the time between printing and handling of the piles and the way that the printed piles of paper are handled after printing.
  • water wipe intaglio inks may be understood to mean inks which are suitable for use in intaglio printing processes that use alkaline wiping solutions.
  • a water wipe intaglio ink may be graded with a score of at least 2, preferably at least 3, when testing according to the Wiping Solution Solubility test using Wiping Solution A defined in the examples.
  • Intaglio ink formulations preferably have excellent durability and pass stringent chemical and physical resistance tests. They would preferably have a long shelf-life and be suitable for drying with siccative driers. These properties are achieved by using varnish systems which are highly tailored for the application and utilize polymeric materials with a wide range of molecular weight and functionality.
  • Intaglio printing inks for security printing are normally composed of an oxidatively curable material, such as an alkyd resin or a modified alkyd resin, a high acid value phenolic resin, pigment, inorganic fillers, rheology modifiers, waxes, emulsifying agent (if required), siccative driers and low boiling point mineral oil distillate to produce a finished product that will adequately solubilise in the alkaline wiping solution on press, exhibit good drying and anti-setoff properties and possess the required chemical resistance specified for that particular document or banknote by the end user.
  • an oxidatively curable material such as an alkyd resin or a modified alkyd resin, a high acid value phenolic resin, pigment, inorganic fillers, rheology modifiers, waxes, emulsifying agent (if required), siccative driers and low boiling point mineral oil distillate to produce a finished product that will adequately solubilise in the alkaline wiping solution on press, exhibit
  • Intaglio ink formulations are traditionally characterized by tack, viscosity and drying time measurements which are well known to those skilled in the art. It is preferred that any change made to one component of the varnish system does not adversely affect these parameters.
  • US6815474B2 refers to a water-based intaglio printing ink having a) an epoxy resin ester reacted with an unsaturated monobasic acid and a reactive monomer, b) a glycol and/or glycol ether c) a pigment, d) a monoalkanolamine, e) a drier and f) water.
  • these efforts to reduce the VOC content of the intaglio inks, or increase the water tolerance of such inks have failed to be widely commercially adopted due to reduced performance compared with conventional intaglio inks.
  • intaglio inks which are based on the use of vegetable oils such as linseed oil, tung oil, dehydrated castor oil, soybean oil or esterified soya bean oils.
  • vegetable oils such as linseed oil, tung oil, dehydrated castor oil, soybean oil or esterified soya bean oils.
  • varnishes and high boiling point solvents preferably with a boiling point higher than 210°C, in a water wipeable, non-smearing intaglio ink composition are mentioned.
  • CN101250352 refers to replacing the mineral oil solvent with soya bean oil which is reacted with other materials at a temperature of 230-300°C to form into ink varnishes.
  • a small amount of free soya bean oil may be used at the end of the production process to adjust the final viscosity.
  • US5569701 refers to a soybean oil-based intaglio ink comprising alkyds synthesised at least in part from soybean oil and tung oil, and/or linseed oil.
  • the soybean oil is reacted with other materials to form an alkyd, so it is not present as a free material.
  • the intaglio ink also contains 0 to 12 % of mineral oil.
  • Another object of the invention is to provide preferred embodiments which exhibit equivalent or improved solubility characteristics in a wide range of sodium hydroxide containing wiping solutions when compared to the low boiling point mineral oil distillate ink formulations currently being used.
  • the invention provides a varnish which is suitable for formulating intaglio inks, comprising a bio-renewable iso-alkane vegetable oil-based solvent, oxidatively curable materials, and high acid value resins, wherein the varnish is mineral oil-free.
  • the invention provides a water wipe security intaglio printing ink composition
  • a bio-renewable iso-alkane vegetable oil-based solvent wherein the ink is mineral oil-free.
  • the invention provides a method of intaglio printing security documents such as banknotes and passports using an ink of the invention.
  • Printed articles obtained from or comprising the ink are also provided.
  • the invention provides use of a bio-renewable iso-alkane vegetable oil-based solvent to prepare a mineral oil-free intaglio ink.
  • iso-alkane type of vegetable oils can be used to replace petroleum-based solvents within intaglio formulations despite having a lower solvency power and higher boiling point when compared to the traditional mineral oil distillates used in the formulation of these types of printing inks.
  • An iso-alkane may be understood as any branched-chain alkane, but especially one having a methyl group attached to the penultimate carbon atom of the main chain.
  • the iso-alkanes are obtained from 100% certified vegetable origin feedstocks, which can be understood to mean they are bio-renewable, but which are then hydrogenated and distilled to give products with a narrow cut of carbon chain lengths and narrow boiling ranges.
  • the carbon chain length of the iso-alkane may be C10-C20, preferably C13-C18.
  • the isoalkane may have an initial boiling point of 120-300°C, 135-250°C, or 200-250°C.
  • the iso-alkane may have a final boiling point of 160-350°C, 180-350°C, 180-280°C, or 200-280°C.
  • the difference between the initial and final boiling point of the iso-alkane may be less than 75°C, less than 50°C, or preferably less than 35°C.
  • Boiling points are typically reported by commercial suppliers. Boiling points may be measured according to ASTM D86-18, e.g. at 101.3kPa. Iso-alkane vegetable oil-based solvents are available from commercial suppliers.
  • the combination of bio renewable isoalkanes of vegetable oil with a carbon chain length of C13-C18 with a naturally occurring drying oil such as refined soya bean oil, refined linseed oil or tung oil enables the formulation of mineral oil-free intaglio inks which are not classified as containing VOC under European Regulation with the correct viscosity and tack, which are suitable for security printing on various substrates, especially banknote substrates.
  • Another advantage of these formulations is that they can perform well in press wiping solutions with lower NaOH concentrations without affecting the quality of print or causing any increase in intaglio plate wear on the press.
  • An alkaline wiping solution based on sodium hydroxide and a surf actant/ detergent in demineralized water is used in the intaglio printing process to remove/wipe any excess ink from the engraved printing cylinder during printing.
  • the waste ink can be treated in the press waste treatment facility.
  • the press wiping solution which has a direct impact on the environment, can contain 1% or more of sodium hydroxide, therefore reducing the amount used will be environmentally more advantageous and desirable.
  • the varnishes and inks may be substantially free of water, for example comprising less than 5 wt% water, or are free from water.
  • the varnishes and inks are preferably not classified as VOC under 2010/75ZEC directive.
  • the varnishes and inks preferably contain less than 1% VOC under 2004/42ZEC directive, for example less than 10 g/1 VOC.
  • the ink may have a viscosity at 40°C of 10-20 Pa s, preferably 12-18 Pa s.
  • the varnish may have a viscosity at 25°C of 15-70 Pa s, preferably 25-60 Pa s.
  • Viscosity may be measured according to ASTM D4287-00.
  • viscosity may be measured with a viscometer, such as a CAP 2000+ Viscometer available from Brookfield Engineering, using a 0.30mL of sample of product, where the equipment setting is Spindle 09 at a speed of 50rpm at 25°C for a varnish and 40°C for an ink.
  • the invention includes a method of making a mineral oil-free varnish suitable for formulating intaglio inks, the method comprising:
  • the inert conditions are typically under an inert atmosphere such as nitrogen, argon, or carbon dioxide. In this way, the mixture is prevented from reacting with oxygen in the air.
  • an inert atmosphere such as nitrogen, argon, or carbon dioxide.
  • step (a) may be to 140-200 °C or 170-190 °C. Typically the heating results in the high acid value resins (which are often obtained in solid form) dissolving in the oxidatively curable materials.
  • step (a) may include agitating the oxidatively curable materials and the high acid value resins, optionally for at least 1 minute, such as from 5 minutes to 1 hour.
  • the materials heated in step (a) may be free from vegetable-based solvents, and may consist of oxidatively curable materials and high acid value resins.
  • vegetable oil-based bio-renewable iso-alkane as the solvent in step (b) avoids the need to include solvents in the heating step (a). This leads to a safer process since it avoids the need to add a solvent, which may be volatile, to a reaction vessel at high temperature.
  • step (b) may be performed, optionally by at least 15 °C and/or to 170 °C or less. In this way, the risk of the solvent vapor igniting is minimized.
  • Step (b) may be performed under inert conditions, again minimizing the risk of the solvent vapor igniting.
  • To facilitate the formation of the varnish step (b) may include agitating the mixture comprising the bio-renewable iso-alkane vegetable oil-based solvent.
  • step (b) the mixture comprising the bio-renewable iso-alkane vegetable oilbased solvent is typically cooled to ambient temperature, when it may then be incorporated into an intaglio ink.
  • the invention provides a method of making a mineral oil-free intaglio ink, the method comprising making a varnish by following the method of making a varnish recited above, and making an intaglio ink comprising the varnish.
  • Making the intaglio ink is typically performed at ambient temperature, typically under ambient atmosphere.
  • Making the intaglio ink typically comprises mixing into the varnish one or more of oxidatively curable materials, high acid value resins, colorants, fillers, rheology modifiers, waxes, emulsifying agents, and siccative driers.
  • the mixing may include triple-roll milling, optionally a pre-mixing step followed by triple-roll milling.
  • Intaglio printing inks for security printing are normally composed of oxidatively curable material, a high acid value resin, colorants, fillers, rheology modifiers, waxes, emulsifying agents, siccative driers and solvents. Details of these components are provided below. It will be understood that these details are relevant to the varnishes, inks, and methods provided by the present invention. Examples of Oxidatively curable materials:
  • the oxidatively curable materials may include linseed or soybean based alkyd of long oil length, medium-oil-length, or short oil length where the acid used may be acid anhydride, phthalic acid, isophthalic acid, diolefinic acid or vinylformic acid and a polyvalent alcohol such as glycerol, pentaerythritol, ethylene glycol, trimethylolpropane or tetramethylolmethane; urethane modified alkyd such as urethane modified soya or linseed oil alkyd; modified soya or linseed oil alkyd; epoxy ester; high acid value alkyd; long chain unsaturated polyacid such as fumaric acid modified vegetable oil and/or drying oils such as tung oil and/or linseed oil.
  • the oxidatively curable materials are selected from the group consisting of linseed and soybean-based alkyds of long oil length, medium-oil-length,
  • Long, medium, and short oil length alkyds are widely used terms which may indicate the fatty acid content of the alkyd.
  • long oil alkyds may contain more than 60 wt% fatty acids
  • medium oil alkyds may contain 40-60 wt% fatty acids
  • short oil alkyds may contain less than 40 wt% fatty acids.
  • the oxidatively curable materials may be present in an amount of 50-80 wt% or 60-70 wt%.
  • the ink may comprise 5-35 wt%, 9-25 wt%, or 12-22 wt% oxidatively curable material.
  • Epoxy esters and/or urethane modified alkyds are particularly preferred oxidatively curable materials.
  • the epoxy ester may be a reaction product of a vegetable oil fatty acid and an epoxy resin.
  • the urethane modified alkyd may be a reaction product of the residual OH groups of a vegetable based liquid alkyd resin and the NCO groups from an isocyanate such as TDI (toluene diisocyanate).
  • the epoxy ester and/or urethane modified alkyd may be present in the varnish in an amount of 2-50 wt%, 4-40 wt%, or 8-30 wt%.
  • the epoxy ester and/or urethane modified alkyd may be present in the ink in an amount of 1-20 wt%, 2-15 wt%, or 2.5-10 wt%.
  • the epoxy ester may be present in the varnish an amount of 2-40 wt%, 4-30 wt%, or 6-20 wt%.
  • the epoxy ester may be present in the ink in an amount of 1-20 wt%, 2-15 wt%, or 2.5-10 wt%.
  • the urethane modified alkyd may be present in the varnish an amount of 5-50 wt%, 15-40 wt%, or 25-30 wt%.
  • the urethane modified alkyd may be present in the ink in an amount of 1-20 wt%, 2.5-15 wt%, or 5-10 wt%.
  • the High Acid Value Resins may include high acid value rosin modified phenolic resin based on gum rosin, paraformaldehyde and/or fumaric acid and/or maleic anhydride and/or pentaerythritol and/or nonylphenol and/or octyl phenol.
  • the acid value of the high acid value resin for example the described high acid value rosin modified phenolic resin, is preferably 100-160 mgKOH/g, more preferably 110-140 mgKOH/g.
  • the high acid value resin may be present in an amount of 20-40 wt% or 20-30 wt%.
  • the ink may comprise 1-30 wt%, or 3-20 wt%, or 6-10 wt% high acid value resin.
  • Acid Value may be determined by titration with 0.1M potassium hydroxide solution using phenolphthalein solution indicator, as is widely known. For example, acid value may be determined by weighing approximately 1.0g of sample accurately (to 2 decimal places) into a clean, dry conical flask and recording the amount used. Approximately 50mL of a 3: 1 mixture of toluene and industrial methylated spirit is then added to the conical flask to dissolve the varnish sample along with 6-8 drops of phenolphthalein solution indicator. Standardized 0.1M potassium hydroxide in methanol is then titrated into the conical flask solution with mixing until a pink color develops and persists for 30 seconds. The Acid Value of the varnish is determined by using the calculation below.
  • the Acid Value result is recorded as milligrams of potassium hydroxide per gram of sample or mg KOH/g.
  • Fillers may include organoclays, fumed silica, aluminum silicate, aluminum hydrosilicate, ground natural calcium carbonate, barium sulphate or fine china clay.
  • the ink may comprise 20-70 wt%, or 30-60 wt%, or 40-50 wt% filler.
  • the colorant may be any pigment that can be employed in printing inks. It may be organic or inorganic and may be a dye or pigment. Typical examples of useable colorants include, but are not limited to, inorganic pigments, such as Pigment White 6 (Titanium Dioxide), Pigment Black 7 (carbon black), Pigment Black 11 (Black Iron Oxide), Pigment Red 101 (Red Iron Oxide) and Pigment Yellow 42 (Yellow Iron Oxide), and organic pigments such as Pigment Yellow 1, Pigment Yellow 3, Pigment
  • Pigment Yellow 98 Pigment Yellow 106, Pigment Yellow 114, Pigment Yellow 121, Pigment 26Yellow 126, Pigment Yellow 136, Pigment Yellow 174, Pigment Yellow 176, Pigment Yellow 188, Pigment Orange 5, Pigment Orange 13, Pigment Orange 16, Pigment Orange 34, Pigment Red 2, Pigment Red 9, Pigment Red 14, Pigment Red 17, Pigment Red 22, Pigment Red 23, Pigment Red 37, Pigment Red 38, Pigment Red 41, Pigment Red 42, Pigment Red 112, Pigment Red 146, Pigment Red 170, Pigment Red 196, Pigment Red 210, Pigment Red 238, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Green 7, Pigment Green 36, Pigment Violet 23 and the like.
  • Suitable inorganic pigments include, but are not limited to, carbon black and titania (TiO2), while suitable organic pigments include, but are not limited to, phthalocyanines, anthraquinones, perylenes, carbozoles, monoazo- and disazobenzimidazolones, isoindolinones, monoazonaphthols, diarylidepyrazolones, rhodamines, indigoids, quinacridones, diazopyranthrones, dinitranilines, pyrazolones, dianisidines, pyranthrones, tetrachloroisoindolinones, dioxazines, monoazoacrylides, and anthrapyrimidines. It will be recognized by those skilled in the art that organic pigments are differently shaded, or even have different colors, depending on the functional groups attached to the main molecule.
  • the dyes include but are not limited to azo dyes, anthraquinone dyes, xanthene dyes, azine dyes, combinations thereof and the like.
  • the ink may comprise 1-15 wt%, or 2-10 wt%, or 3-7 wt% colorant.
  • additives may be incorporated to enhance various properties.
  • a partial list of such additives includes but is not limited to adhesion promoters, silicones, light stabilizers, optical brighteners, de-gassing additives, ammonia, flow promoters, defoamers, antioxidants, stabilizers, surfactants, dispersants, plasticizers, rheological additives, waxes, silicones, etc.
  • Solvents for security inks may include vegetable oil (e.g. soya bean oil, castor oil, rapeseed oil, linseed oil, tung oil), mineral oil, aliphatic hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, ketones, aldehydes, alcohols, ethers, esters. Drying oils such as linseed oil and tung oil may act as both solvents and as oxidatively curable materials.
  • vegetable oil e.g. soya bean oil, castor oil, rapeseed oil, linseed oil, tung oil
  • mineral oil e.g. soya bean oil, castor oil, rapeseed oil, linseed oil, tung oil
  • mineral oil e.g. soya bean oil, castor oil, rapeseed oil, linseed oil, tung oil
  • mineral oil e.g. soya bean oil, castor oil, rapeseed oil, l
  • the invention utilizes bio-renewable iso-alkane vegetable oil-based solvents.
  • the varnish may comprise 5-30 wt% or 10-20 wt% bio-renewable iso-alkane vegetable oil-based solvent.
  • the ink may comprise 2-50 wt%, or 4-30 wt%, or 6-20 wt% biorenewable iso-alkane vegetable oil-based solvent.
  • Co-solvents which are preferably bio-renewable, many include refined soya bean oil, rapeseed oil, castor oil, refined linseed oil and tung oil.
  • the varnish may comprise l-15wt% or 5-10wt% of a bio-renewable co-solvent.
  • the ink may comprise 0.5-20 wt% or 1-10 wt% of a bio-renewable co-solvent.
  • a varnish which is suitable for formulating intaglio inks comprising vegetablebased solvent, oxidatively curable materials, and high acid value resins, and wherein the varnish comprises ⁇ 1% VOC, more preferably VOC-free, and is mineral oil-free.
  • oxidatively curable materials are selected from the group consisting of linseed and soybean-based alkyds of long oil length, medium-oil-length, and short oil length or epoxy ester and combinations thereof.
  • the high acid value resins are selected from the group consisting of high acid value rosin modified phenolic resin based on gum rosin, paraformaldehyde and/or fumaric acid and/or maleic anhydride and/or pentaerythritol and/or nonylphenol and/or octyl phenol with an acid number preferably of 110-160 mgKOH/g, more preferably 110-140 mgKOH/g, and combinations thereof.
  • bio-renewable vegetable oil is selected from the group consisting of linseed oil, soya bean oil, castor oil, rapeseed oil, linseed oil, tung oil and combinations thereof.
  • An intaglio ink comprising the varnish of any one or more of paragraphs 1-8.
  • Example l is a comparative example using conventional mineral oil Exxsol D60.
  • Example 2 is a comparative example using an unsaturated linseed oil fatty acid ester Cl 6- 18 to replace the mineral oil with an alternative bio-renewable solvent which is shown to be not suitable for intaglio printing.
  • Example 3 modifies Example 1 into an inventive example using as the solvent a C13- C18 bio-renewable iso-alkane derived from vegetable oil having a difference between the initial and final boiling points of about 25°C.
  • Example 4 modifies Example 3 by adding drying oil as a co-solvent
  • Example 5 replaces the long oil length alkyd with epoxy ester into the invention
  • Example 6 utilises a combination of long oil length alkyd and epoxy ester resin into the invention.
  • Example 7 utilises modified alkyd, high acid value alkyd and resin emulsifier into the invention.
  • Example 8 utilises urethane alkyd, high acid value alkyd and resin emulsifier into the invention.
  • Example 9 is a comparative example based on Example 1 but using refined linseed oil instead of mineral oil.
  • Example 10 is a comparative example based on Example 5 but using refined linseed oil instead of bio-renewable iso-alkane.
  • Example 11 is an inventive example based on Example 5 but using a bio-renewable iso-alkane derived from vegetable oil which has a carbon chain length of C11-C13 having a difference between the initial and final boiling points of about 20°C.
  • Example 12 is a comparative example based on Example 1 where the the Exxsol D60 mineral oil solvent is replaced with a high boiling mineral oil solvent, boiling range 275 - 320°C.
  • Examples 13 - 24 are intaglio inks which use the above varnishes.
  • the varnishes are prepared by mixing the oxidatively curable materials (e.g. alkyd components, long chain polyacid and epoxy ester) together in accordance with the formulations in the examples and heating to 180°C under inert gas.
  • the resin e.g. modified phenol formaldehyde resin
  • the mixture is stirred until the resin is completely dissolved.
  • the mixture is cooled to 160°C and the requisite solvents in the formulations are added.
  • the mixture is allowed to cool to room temperature before incorporating into an intaglio ink
  • Example 1 (Comparative) Mineral Oil Based Intaglio Varnish
  • Example 3 (Inventive) Iso-alkane-based Intaglio Varnish
  • Example 7 (Inventive) Iso-alkane-based varnish
  • Example 8 (Inventive) Iso-alkane-based varnish
  • Example 9 (Comparative) Vegetable oil-based varnish
  • Example 10 (Comparative) Vegetable oil-based varnish
  • Example 11 (Inventive) Iso-alkane-based varnish - alternative iso-alkane
  • Example 12 (Comparative) High Boiling Mineral Oil-Based Varnish
  • Viscosity, tack and solids content was measured for the above varnish examples using the following test methods: VISCOSITY: Measured with a CAP 2000+ Viscometer using a 0.30mL of sample of product. The equipment setting was Spindle 09 at a speed of 50rpm at 25°C.
  • TACK Measured using the Protack Tack Meter. Varnishes were tested using l.OmL of sample with the machine set to Program 4 @ 25°C.
  • SOLIDS CONTENT OF VARNISHES The solids content was determined using a Sartorius MA35 Solids Content Testing Unit. 0.5g of varnish sample was accurately weighed onto a foil square on the Sartorius MA35 unit which had been set at a temperature setting of 160°C for a duration of 30 minutes. The lid is then closed to start the test and the solids content of the varnish sample automatically indicated after the test is completed on a digital readout.
  • Table 1 exhibits the fitness for use for all of the inventive examples (Examples 3-8 and 11) in terms of tack. As is known to those skilled in the art; viscosity and solids content can be further adjusted by suitable solvent additions, so all the inventive examples were suitable for incorporation into intaglio printing inks.
  • the varnish examples in Table 1 were incorporated into a standard intaglio ink formulation detailed in the examples below. Approximately 400g sized batches of inks were produced by premixing all materials on a laboratory tri-foil mixer for approximately 15 minutes until a smooth paste had been achieved. The pre-mix was then given two passes through a small production triple roll mill at medium setting conditions (15psi, front and back roller settings). Particle size was checked on a 50pm Sheen grinding gauge. If there was scratching above 10pm further milling would be required. In the comparative ink formulations based on refined linseed oil (Example 21 and Example 22), additional refined linseed oil was required to achieve suitable viscosity and tack for testing purposes.
  • Example 13 (Comparative) Intaglio Ink Formulation using Example 1 Mineral Oil
  • Example 14 (Comparative) Intaglio Ink Formulation using Example 2 Fatty Acid Ester of Vegetable Oil Based Intaglio Varnish
  • Example 15 (Inventive) Intaglio Ink Formulation using Example 3 Iso- Alkane Based
  • Example 16 (Inventive) Intaglio Ink Formulation using Example 4 Iso-Alkane Based
  • Example 17 (Inventive) Intaglio Ink Formulation using Example 5 Iso-Alkane Based Intaglio Varnish
  • Example 18 (Inventive) Intaglio Ink Formulation using Example 6 Iso-Alkane Based
  • Example 19 (Inventive) Intaglio Ink Formulation using Example 7 Iso-Alkane Based
  • Example 20 (Inventive) Intaglio Ink Formulation using Example 8 Iso-Alkane Based
  • Example 21 (Comparative) Intaglio Ink Formulation using Example 9 Vegetable Oil Based Intaglio Varnish
  • Example 22 (Comparative) Intaglio Ink Formulation using Example 10 Vegetable Oil
  • Example 23 (Inventive) Intaglio Ink Formulation using Example 11 Iso- Alkane
  • Example 24 (Comparative) Intaglio Ink Formulation using Example 12 High Boiling Point Mineral Oil Based Intaglio Varnish
  • Viscosity, tack, drying time and solubility in wiping solution was measured for the above intaglio ink examples using the following test methods:
  • VISCOSITY Measured viscosity on a CAP 2000+ Viscometer using a 0.30mL of sample of product. The equipment setting was Spindle 09 at a speed of 50rpm. Intaglio inks are tested at 40°C.
  • Tack is measured using the Protack Tack Meter. Intaglio inks are tested using a 2.0mL sample with the machine set to Program 4 at 40°C.
  • INK DRYING TIME The drying times of the Intaglio Permanent Carmine Ink preparations were tested on the TQC Sheen Drying Recorder. A 25 p film of ink was applied to a large glass slide using a film applicator, the machine set to zero, the needle applied to the ink surface and the recorder switched on. The ink drying time is recorded as being the point where the needle no longer makes a mark in the ink film on the glass slide.
  • WIPING SOLUTION SOLUBILITY Wiping Solution is placed into a 500ml glass beaker, a magnetic stirrer bar added and the contents heated under stirring on a hot plate mixer to 40°C. Approximately 1.0g of each of the ink samples is applied to the inside of a 50ml glass measuring cylinder, near the top, and the 40°C wiping solution poured into the measuring cylinder to the top. The time when the ink first started to precipitate in the wiping solution (in seconds) is recorded along with the ability for the ink to precipitate in the solution graded from 1 to 5 using the following criteria:
  • Drying time 12-20 hr.
  • Table 2 exhibits the fitness for use as printing inks for of the inventive examples 10 (Examples 15-20 and 23) in terms of setting properties, viscosity, tack and wiping solution solubility. In particular they show satisfactory drying, setting characteristics and solubility in press wiping solutions with lower NaOH concentrations. This means that the inks are suitable for printing on commercial intaglio printing presses and will give good quality prints without set-off defects.
  • Example 15 The raw materials in Examples 17 and 18 were manipulated to achieve the required setting and drying properties in the intaglio ink formulation.
  • Manipulation of the raw materials in a varnish formulation means that the percentages of each component are adjusted to obtain the required rheology, setting and drying properties in the final ink.
  • examples using iso-alkane vegetable-based solvent were found to have improved properties for use as intaglio inks compared to the comparative examples using the vegetable-based solvents Fatty Acid Ester of Vegetable Oil and Refined Linseed Oil (Examples 14, 21, and 22), in particular improved drying time and setting speed.
  • This demonstrates the improvement provided by the invention in comparison to other mineral oil-free formulations utilizing vegetable-based solvents.
  • Demineralised Water 90.0% formulation for James Heal ECE non-Phosphate
  • Table 3 exhibits the fitness for use of final documents printed using the inventive examples (Examples 15-20 and 23) in terms of physical and chemical resistance. These tests measure the performance of the printed ink against a range of circulation hazards that banknotes may be exposed to.
  • Example 19 showed slightly reduced rub resistance compared to typical properties for an intaglio ink. This means that it may show more wear in a harsh circulating environment but would give acceptable performance on other value documents.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Printing Methods (AREA)

Abstract

La présente invention concerne une composition d'encre hélio d'impression de sécurité et d'essuyage à base d'eau comprenant, en tant que composant principal, un solvant à base d'huile végétale iso-alcane bio-renouvelable, qui, en combinaison avec d'autres constituants, produit une encre exempte d'huile minérale ayant une durabilité améliorée et une empreinte environnementale réduite lorsqu'elle est comparée à des formulations existantes conçues pour la même application.
PCT/GB2022/053381 2021-12-24 2022-12-23 Encre hélio exempte d'huile minérale WO2023118897A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP22840280.6A EP4430132A1 (fr) 2021-12-24 2022-12-23 Encre hélio exempte d'huile minérale
AU2022421027A AU2022421027B2 (en) 2021-12-24 2022-12-23 Mineral oil-free intaglio ink
CONC2024/0009418A CO2024009418A2 (es) 2021-12-24 2024-07-17 Tinta calcográfica sin aceite mineral

Applications Claiming Priority (4)

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US202163293671P 2021-12-24 2021-12-24
US63/293,671 2021-12-24
GB202200325 2022-01-12
GB2200325.5 2022-01-12

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US4404251A (en) * 1980-03-26 1983-09-13 Bayer Aktiengesellschaft Copying systems, a process for their production, and suitable printing inks for both offset and book printing
US5569701A (en) 1995-05-31 1996-10-29 Bureau Of Engraving And Printing Soybean oil-based intaglio ink and method for making same
US6815474B2 (en) 1995-06-13 2004-11-09 Sun Chemical Corporation Water-based intaglio printing ink
CN101250352A (zh) 2008-03-26 2008-08-27 中国印钞造币总公司 大豆油基凹印油墨及其连接料
CN101386724A (zh) 2001-12-25 2009-03-18 樊官保 植物油、调墨油和高沸点溶剂在水擦不蹭脏雕刻凹版印刷油墨组合物中的用途
JP5467556B2 (ja) 2009-04-01 2014-04-09 東京インキ株式会社 平版印刷用インキおよびそれを用いて印刷した印刷物
WO2015024966A1 (fr) 2013-08-21 2015-02-26 Oleon N.V. Encres pour impression sur caoutchouc comprenant un solvant d'ester d'acide gras d'isosorbide
KR20160080339A (ko) * 2014-12-29 2016-07-08 한국조폐공사 수불식 요판잉크 및 이의 제조방법
WO2019129625A1 (fr) * 2017-12-29 2019-07-04 Neste Oyj Distillat renouvelable hautement isoparaffinique à usage de solvant

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4404251A (en) * 1980-03-26 1983-09-13 Bayer Aktiengesellschaft Copying systems, a process for their production, and suitable printing inks for both offset and book printing
US5569701A (en) 1995-05-31 1996-10-29 Bureau Of Engraving And Printing Soybean oil-based intaglio ink and method for making same
EP0745652A2 (fr) * 1995-05-31 1996-12-04 U.S. Department Of Commerce Encre héliographique à base d'huile de soja et son procédé de préparation
US6815474B2 (en) 1995-06-13 2004-11-09 Sun Chemical Corporation Water-based intaglio printing ink
CN101386724A (zh) 2001-12-25 2009-03-18 樊官保 植物油、调墨油和高沸点溶剂在水擦不蹭脏雕刻凹版印刷油墨组合物中的用途
CN101250352A (zh) 2008-03-26 2008-08-27 中国印钞造币总公司 大豆油基凹印油墨及其连接料
JP5467556B2 (ja) 2009-04-01 2014-04-09 東京インキ株式会社 平版印刷用インキおよびそれを用いて印刷した印刷物
WO2015024966A1 (fr) 2013-08-21 2015-02-26 Oleon N.V. Encres pour impression sur caoutchouc comprenant un solvant d'ester d'acide gras d'isosorbide
KR20160080339A (ko) * 2014-12-29 2016-07-08 한국조폐공사 수불식 요판잉크 및 이의 제조방법
WO2019129625A1 (fr) * 2017-12-29 2019-07-04 Neste Oyj Distillat renouvelable hautement isoparaffinique à usage de solvant

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AU2022421027A1 (en) 2024-06-27
CO2024009418A2 (es) 2024-07-29

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